Quinoline azo dye



United States Patent 3,244,693 QUINOLINE AZO DYE Ernest M. May, Summit, and Andrew Fono, Montclair, N.J., assignors to Otto B. May, Inc., Newark, N.J., a corporation of New Jersey No Drawing. Filed Mar. 13, 1963, Ser. No. 264,760 Claims. (Cl. 260-155) This invention relates to new dyes; and, more particularly, it is concerned with compounds which are especially suitable for dyeing shaped articles of polyolefins, such as polypropylene, and other hydrophobic thermoplastic resins, such as polyesters, polyacrylics and polyamides.

Many known classes of dyes have been applied to polypropylene and other polyolefins in an attempt to dye these materials in a commercially satisfactory way, that is to say, to yield a dyed product which is fast to washing and dry cleaning. Those classes of dyes which are water-soluble are for this very reason unsuitable for dyeing polypropylene. The water solubility of these dyes means inherently that they are insoluble in polypropylene, and even if a surface dyeing is achieved they are readily removed by washing. Furthermore, the dyes which are soluble in polypropylene (a fundamentally hydrocarbon polymer) are also soluble in dry cleaning solvents and those dyes which have afiinity for polypropylene are generally removed by dry cleaning solvents.

An obiect of the present invention is to obtain dye compositions which are suitable for dyeing polypropylene and other polyolefins. Y

Another object of the invention is to obtain dyes which can be used for dyeing other thermoplastic resins, such as polyesters, polyacrylics, cellulose triacetate and polyamides.

It is common practice in the textile industry to form composite fabrics containing wool and a synthetic thermoplastic polymeric resin. For example, a composite fabric may be woven of threads containing, in a predetermined pattern, threads of wool and polypropylene or some other thermoplastic fiber. In the past, many classes of dyes have been applied to these composite fabrics to give a union dyeing. In other words, both the wool and the thermoplastic fiber are dyed to the same hue using normal dyeing procedures. However, this is unsuitable in certain commercial aspects where it is desired to dye the thermoplastic fiber in the composite fabric without dyeing the Wool fiber therein.

Accordingly, another object of this invention is to provide a composite mixed fabric of wool fibers and polyolefin, e.g., polypropylene, fibers or other thermoplastic fibers and to produce dyes which will dye the thermoplastic fibers therein and which will not substantially stain or dye the wool therein employing the usual dyeing techniques.

A further object of the present invention is to provide dyes which are fast to washing and severe dry cleaning when applied to synthetic shaped articles, particularly fibers containing finely dispersed metallic compounds.

One of the very difiicult problems that has confronted the industry is stabilizing polypropylene and other polyolefin fibers against ageing, that is, degradation caused by exposure to air, light, and/or heat. Many types of known stabilizers have been incorporated into the fibers to impart some degree of stability thereto. However, these stabilizers generally are removed by washing and/ or dry cleaning with various solvents, and the fibers lose most or all of their resistance to ageing.

Accordingly, still another object of this invention, is to stabilize shaped articles formed from polypropylene and other polyolefins and preferably simultaneously stabilize and pigment such materials.

Another object is to improve stability and the resistance of these polymers to ageing, particularly after they have been washed, dry cleaned or exposed to other solvents.

Other objects and advantages of the present invention will appear from the following description.

The dyes, which according to the present invention have been found to be particularly suitable for dyeing polypropylene and other polyolefins, are certain substituted disazo 8-quinolinol compounds described by the following structural formula:

wherein each X is a substituent group attached to the benzene nucleus independently selected from the group consisting of cycloalkyl having up to 6 carbon atoms, 2,3-benz, nitro, halogen, acyl having up to 6 carbon atoms, benzoyl, N-alkylsulfonamido said alkyl containing 1-5 carbon atoms, N,N-dialkylsulfonamido each of said alkyls containing 1-5 carbon atoms, alkoxy containing 1-4 carbon atoms, trifluoromethyl, cyano, benzoylamino, carboalkoxy containing l-4 carbon atoms, dialkylamino each of said alkyls containing 1-5 carbon atoms, hydroxy, arylazo, beta-cyanoethyloxy, beta-hydroxyethyloxy, methylsulfonyl, thio cyano, di (beta hydroxyethyl)- amino and di-(beta-cyanoethyl)-amino; each Y is a substituent group attached to the benzene nucleus independently selected from the group consisting of cycloalkyl having up to 6 carbon atoms, 2,3-benz, alkoxy containing 1-4 carbon atoms, beta-hydroxyethyloxy, beta-cyanoethyloxy, halogen, and trifiuoromethyl; R and R are alkyl groups having 1 to 5 carbon atoms; Z is selected from the group consisting of hydrogen and methyl; a is an integer from 0 to 3 inclusive; b is an integer from 0 to 2 inclusive; n is an integer from 0 to 4 inclusive; m is an integer from 0 to 4 inclusive; and a-l-b must be at least 1. It is noteworthy that the sulfonic acid group (SO H) is not included as a substituent group for either X or Y in the above structure. It is important for the success of this invention that the substituted disazo S-quinolinol dye compounds are free from sulfonic acid groups.

The foregoing groups for X and Y in the structure may be substituted with simple substituents recognized in the dyeing art, such as C to C alkyl, e.g., methyl, nitro, halogen, C to C alkoxy, e.g., methoxy, trifiuoromethyl, carbonamido and the like.

Preferred substituted disazo 8-quinolinol compounds are found among those in which the group or groups X or Y include at least one trifluoromethyl group, or at least one halogen (fluorine, chlorine, or bromine), or at least one lower alkoxy group (1 to 4 carbon atoms); compounds in which the group or groups X include at least one nitro group or the arylazo group; or compounds in which the group or groups X or Y include the 2,3-benz group, such as 5-naphthaleneazobenzeneazo-S-quinolinol.

The aforementioned disazo dyes can be prepared by any known method. However, they are generally formed by coupling an aminoazo benzene through diazotization with an 8-quinolinol. vThe aminoazo benzenes can be provided by rearrangement of a diazoamino compound; by coupling a diazonium compound with an aniline derivative; or by coupling the diazonium compound with a N methane sulfonic acid salt of an aniline derivative and subsequently hydrolyzing the resulting product with aqueous alkali. In some instances, it may be necessary to use a solvent other than pure water to provide better solubility of the diazotized aminoazo compound and provide greater coupling speed. Dimethylforamide is an example of a neutral solvent for the diazotization and coupling of relatively insoluble aminoazo compounds with S-quinolinol. A finely dispersed paste is preferably formed from the resulting dyestuff, for example, by milling in the presence of a dispersing agent.

In one embodiment, a synthetic shaped article, for example, a fiber, has a metal incorporated therein before a substituted 8-quinolino1 compound is applied. In another embodiment of the present invention, the synthetic fiber is not modified with a metallic material. The unmodified or modified synthetic fibers or other shaped articles applicable to this invention include polyolefins, polyesters, for example, condensation products of polybasic acids with polyhydric alcohols and Dacron; polyamides, such as nylon; polymers of acrylic acid compounds, such as acrylonitrile; polymers of vinyl compounds, such as vinyl alcohol, vinyl chloride and styrene; polyacetals, such as polyformaldehyde; and cellulose triacetate. A polyolefin, which is a preferred polymer for a synthetic fiber, includes the following polymers among others: polyethylene, polypropylene, polybutene, poly-3-methyl-butene-1, polypentene, poly-4-methyl-pentene-l, and polyheptene. The polyolefin, e.g., polypropylene, can be prepared by any known method.

Synthetic shaped articles are formed from one or more of the aforementioned thermoplastic polymers or from one or more of these polymers in combination with wool as a composite fabric in accordance with known prior art procedures. A fiber, which is preferred, is defined herein as any fibrous unit, for instance, filament yarns, mats, staple yarns, rovings, sheets, rods, plates, woven fabrics and chopped fibers. The following exemplify specific commercial fibers which can be employed herein: Spun Dacron T-54, Nylon Filament Thread, Cresland T58, Acrilan 1656, Polypropylene 805 Fiber, and Arnel, manufactured by Celanese Corporation of America.

The substituted disazo 8-quinolinol dye compounds heretofore described form the basis of an aqueous dye bath into which the fibers are immersed. Since the dyes are insoluble in water, they must be dispersed in the bath. Any known dyeing technique may be employed in this invention, including the methods discussed and referenced in the article by Fortess, Advances in Textile Processing, vol. 1, pages 333-373, to provide a dyed fiber therefrom.

As stated heretofore, the synthetic shaped article, e.g., a fiber, may be modified with a metallic material. As defined in this invention, a metal modified synthetic shaped article is one which contains additional metal therein besides the metal that may be present as residual catalyst from the preparation of the synthetic thermoplastic polymer itself. This added metal in the fiber forms a reaction product with the subsequently applied dye composition. Although the precise nature and structure of the aforementioned reaction product is not clearly understood, it is possible that a chelate ring or linkage is formed between the metallic cation and the hydroxyl group on the S-quinolinol ring. However, the amount of dye employed for the reaction with the metal and the ratio of fiber to metal are not critical features of this invention.

Any suitable metal or more than one metal may be incorporated into the synthetic fiber or other shaped article. Aluminum, nickel, chromium and zinc are the preferred metals, and they are utilized as metallic compounds. Organic metal salts, for example, may be employed within the range of .02 to .2% based upon the weight of the fiber. Carboxylic acid metal salts with 6 to 20 carbon atoms, which are preferred for this invention, include aluminum stearate, zinc stearate, aluminum laurate, the aluminum salt of 2-ethylhexanoic acid and mixtures thereof.

The fiber may be modified with the aforementioned metallic materials by any satisfactory method. A satisfactory but not the only method (as disclosed in Belgian Pat. No. 617,280) is to intimately disperse an organic metal salt throughout the polymer at any stage prior to i its extrusion. An efficient blending apparatus is usually adequate to accomplish this result. A'fter dispersion the blend may be extruded at the fluid temperature for the polymer, i.e., 250 to 350 C. for polypropylene. Accordingly, the metal is usually distributed uniformly throughout the fiber, e.g., polyolefin fiber, which provides complete penetration of the dye from the dye bath into the fibers. By way of illustration, the incorporation of the metal salt in the polymer may be made by mixing 10 parts of the powder of the salt with 90 parts of the powder of the polymer to an intimate and uniformly dispersed mixture. This mixture may be extruded to form a concentrate which subsequently is finely divided again and intimately blended with additional polymer to obtain the desired low concentration of metal for extrusion to the shaped product.

It is also within the purview of this invention, to react the aforementioned substituted disazo 8-quinolinol compound with the metallic material in solution without any shaped article, such as fiber, being present. A pigment is formed thereby which can be recovered and used as a pigment in a manner known in the art.

Thus, in accordance with the instant invention substituted disazo 8-quinolinol compounds have been provided which are suitable dyestuffs. compounds will react with metal-modified shaped articles to form a dyed end product which is fast to light, dry cleaning and washing. Similarly, these com-pounds can be applied directly to dye an unmodified fiber since, for

example, nylon, polyester, cellulose triacetate and acrylic fiber-s have polar groups which can form a polar linkage with the present dyes to improve the receptivity of the dye and the fastness properties.

The superior light fastness of the dye on the metal modified or unmodified shaped article is a first surprising feature of this invention. Secondly, it is surprising that the instant substituted disazo S-quinolinol compounds also impart stability to the polyolefin fibers and other shaped articles and resist removal by laundering, dry cleaning and the like. A third surprising feature is the fact that dye compounds with two or more substituents,

besides alkyl substituents, for X or Y are soluble in polypropylene or other polyolefin fibers. Fourthly, it is indeed unexpected and surprising that if a composite, mixed fiber of wool and a thermoplastic polymer, such as polypropylene, is placed in the usual aqueous dye bath with the instant substituted disazo 8-quinolinol compounds therein, the thermoplastic polymer portion in the composite fabric is dyed but the wool portion in the composite fabric is substantially undyed.

The following examples are submitted to illustrate but.

not to limit this invention. Unless otherwise indicated, all parts and percentages in the specification are based upon weight.

EXAMPLE I A 5 (benzeneazo 2,5 dimethoxybenzeneazo) 8- quinolinol dyestuif was provided by adding at 70 C. 39.3 parts (2.57 moles) 2,5-dimethoxyaniline to 625 parts water and 32.3 parts (2.8 moles) concentrated hydrochloric acid to form a first solution. The temperature of this solution was maintained at 70 C. for one hour with subsequent cooling to 25 C.

A second and separate solution was provided from 256 parts (2.76 moles) aniline, 250 parts water and parts (6.7 moles) concentrated hydrochloric acid. This second solution was stirred until the aniline was completely dissolved, and it was then cooled to 0-5 C. by the addition of 250 parts ice. In the next 15 minutes, 20 parts (2.9 moles) sodium nitrite dissolved in 70 parts Water were added to the cooled solution with stirring until there Furthermore, these was no free aniline present. The excess sodium nitrite was then destroyed by adding sulfamic acid thereto.

A third solution was provided consisting of 32.4 parts (4 moles) sodium acetate in 140 parts water. This third solution was added over a period of one hour to the first solution which was previously cooled further to C. After minutes from the beginning of the addition of the third solution to the first solution, the second solution was added slowly thereto; this addition was stopped when there was a negative test for 2,5-dimethoxyanline in the first solution.

After the coupling was completed, 22 parts (1.9 moles) concentrated hydrochloric acid were added at a temperature of 10-12 C. and subsequently over a period of one hour 21 parts (3.04 moles) sodium nitrite dissolved in 140 parts water were added. The fourth solution therefrom was kept at a temperature of 10 C. for a period of 3 hours, and it was then clarified by filtration.

A fifth and separate solution was formed consisting of 1200 parts water and 20.4 part-s (2.7 moles) 50% hydrochloric acid and 35 parts (2.4 moles) 8-quinolinol were added thereto at a temperature of 50 C. After one half-hour at 50 C., acetic acid was added until the pH dropped to 7.3 and then 119 parts (14.4 moles) sodium acetate were added. The fifth solution was then cooled to C. and the aforementioned fourth solution was then added slowly thereto until there was a negative test for S-quinolinol. The dyestutf therefrom was filtered ofl? and the presscake was milled to a finely dispersed product.

Fiber grade polypropylene, which was blended intimately and uniformly with 0.080 wt. percent of aluminum monostea-rate, was used to manufacture 4 /2 denier crimped staple fiber by melt extruding, stretching, crimping, and cutting to a 2 in. length. This cut fiber was subsequently carded and spun to produce yarns approximating .10s single (cotton system) count. Convenient sized skeins were then reeled from this yarn.

A sample containing ten grams of skein was provided. This sample was immersed in a 500 cc. dye bath at 120 F. The bath consisted of an aqueous dispersion of 0.6 gram of the dry aforementioned dyestutf. Prior to the entry of the yarn, sufficient acetic acid was added to the dye bath to provide a pH of 6.0 The dyeing was accomplished by gradually raising the temperature of the dye bath to its boiling point during a 30 minute period. The skein was frequently turned with a glass stirring rod and the temperature was maintained at 212 F. for a period of one hour. The yarn was then removed from the dye bath and thoroughly rinsed in running water at 160 F. The skein was subsequently scoured by turning it for 30 minutes at 160 F. in a 400 cc. aqueous bath containing /2% of Triton X-100 (iso-octyl-phenyl poly ethoxy ethanol) and /2% of sodium carbonate. A thorough rinse was subsequently performed in running water at 110 F.

The dyed sample was then subjected to the following tests.

(1) Color fastness to dry cleaning: Tentative Test Method 85-1960 (1960 Technical Manual of the American Association of Textile Chemists and Colorists, pages 88-9) amended as follows: the temperature shall be 115 F.; the time shall be 1 hour; and the amount of perchlorethylene shall be 200 cc.

(2) Color fastness to washing (polypropylene): Tentative Test Method 61-1960, Test Number III-A (1960 Technical Manual of the American Association of Textile Chemists and Colorists, pages 93-4). In each instance, the dyeings shall rate (for polypropylene) as follows: for color loss, class 5; for staining, class 3 or better.

(3) Color fastness for washing (synthetics): AATCC Tentative Test Method 61-1961 T (page 105 10c. cit.)

6 with Test III-A being used for polyester and afterchromed nylon and Test II-A for nylon.

(4) Color fastness to light: AATCC Standard Test Method 16-A, 1960 (page 10c. cit.).

(5) Color fastness to oxides of nitrogen in the atmosphere: Three cycles were used of Standard Test Method 23-1957 (page 98 10c. cit.) or Standard Test Method 75-1956 (page 100 10c. cit.).

(6) Sublimation and heat fastness tests: Sublimation and heat fastness tests were run at 265 F. for 15 minutes.

The dyed polypropylene had a red shade and it had excellent fastness properties.

EXAMPLE II A Dacron fiber Was dyed with the dye of Example I by providing a bath of 180 F. containing 200 parts water and 1.5 parts of a blend of 67% biphenyl and 33% aninonic emulsifier. Ten grams of skein were incorporated for a five to ten minute run. The aforementioned dye, which had been previously pasted and dispersed in 100 parts water, was added and the temperature of the bath was raised to boil for 1 to 1% hours. The following procedures were subsequently employed: rinsing for 5 minutes in a fresh bath heated as rapidly as possible to to 200 F.; dropping without cooling; and scouring at 200 F. for 15 to 20 minutes.

The dyed Dacron fiber had a red-brown shade and had excellent fastness properties.

EXAMPLE III Dye No A-Ring B-Ring Shade Substituents Substituents 2,5-di-OCH Red. Red. Red-orange.

Violet.

Having set forth the general nature and specific embodiments of the present invention, the scope is now particularly pointed out in the appended claims.

We claim:

1. A dye composition having the structure:

(X) n (Y)b wherein each X is a substituent group attached to the benzene nucleus independently selected from the group consisting of 2,3-benz, nitro, fluoro, chloro, bromo, alkoxy containing 1-4 carbon atoms, trifluoromethyl and phenylazo; each Y is a substituent group attached to the benzene nucleus independently selected from the group consisting of 2,3-benz, alkoxy containing 1-4 carbon atoms, fiuoro, chloro, bromo and trifluoromethyl; a is an integer from 0 to 2 inclusive; b is an integer from 0 to 2 inclusive; and a+b must be at least 1.

2. The dye composition according to claim 1 in which X is nitro and Y is fiuoro.

3. The dye composition according to claim 1 in which X is chioro and Y is C to C, alkoxy.

4. The dye composition according to claim 1 in which X is trifiuoromethyl and Y is 2,3-benz.

5. The dye composition according to claim 1 in which X is phenylazo and Y is 'trifiuoromethyl.

6. The dye composition according to claim 1 in which X is 2,3-benz and Y is bromo.

7. The dye composition which is 5-(benzcneazo-2,5- dirnethoxybenzeneazo -8-quinolino1.

8. A dye composition which is 5-benzeneazo-naphtha1- eneazo-S-quinolinol.

9. A dye composition which is S-benzeneazo-benzeneazonaphthaleneazo-8-quino1ino1.

2,S-dimethoxybenzeneazo) -8-quino1ino1.

' References Citedby the Examiner UNITED STATES PATENTS 2,096,722 10/1937 Andersen 260-148 2,764,466 9/1956 Bigood 8-21 2,861,066 11/1958 Andres 26O155 2,869,968 1/1959 Thumrnel 821 3,117,959 1/1959 Dehnert 260-155 I FOREIGN PATENTS 158,409 4/1940 Austria.

CHARLES B. PARKER, Primary Examiner.

NORMAN G. TORCHIN, Examiner. 

1. A DYE COMPOSITION HAVING THE STRUCTURE: 